Temperature-regulating system



April 17, 1928.

c. E. ANDREWS TEMPERATURE REGULATTNG mm Filed Feb 19. 1927 5 Sheets-Sheet 1 INVENTOR 619557512 E/Nmfms ff/W A TTORNEYJ c. E. ANDRE W8 TEMPERATURE REGULATING SYSTEM April 17, 928.

Filed Feb. 19,1927 5 Sheets-Sheet 2 m6 m M M Z 10 gym A E R w April 17, 1928.

C. E. ANDREWS TEMPERATURE REGULATING SYSTEM ,Filed Feb. 19. 1927 5 Sheets-Sheet s INVENTOR 6715975? 5 fl/Vfi/PEWG BY 6 W ATTORNEYS llll l April 17, 1928 C. E. ANDREWS TEMPERATURE REGULATII IG SYSTEM Filed Feb. 19, 1927 5 Sheets-Sheet 4 April 17, 1928.

- C. E; ANDREWS TEMPERATURE REGULATING SYSTEM Filed Feb. 19, 1927 5 Sheets-Sheet 5 WWW A TTORNE Y5 Patented Ap -.17, 1928.

UNi Eo-sTA'TEs P CHESTER E. ANDREWS, ()Ili CARNEGIE, PENNSYLVANIA COMPANY, OF PITT SBURGH,

,eeazsi PENNSYLVANIA, A GORPORATION OI DELAWARE.

rnmrmrunn-nneunnrme SYSTEM.

Application filed February 19, 1927. Serial No. 168,572.

This invention relates ulating temperature by liquids and more partic lmproved method to methods of regthe use of boiling ularly relates to an of controlling mtermit tently or continuously the boiling point of high boiling mixtures.

In the past theme of boiling liquids for the control of temperatures, particularly of chemical reactions, has important, especially in tainvapor phase catalyt become exceedingly connection with cer- 1c reactions, such as the oxidation of aromatic compounds to intermediate oxidation products, pyrogenetlc processes, such as cracking of oils;

drogenation, anone from dehysuch as production of cyclohexcyclohexanol dehydration;

polymerization, and condensation, such as production of artificial resins and other reactions whi temperature control.

like cumarone ch require an exact Reactions can be car ried out at atmospheric, diminished or elevated pressure.

as mercury, have temperature actions and for similar High boiling liquids, such been used to regulate the in converters for catalytic repurposes but labor under the disadvantage that when variations in temperature are required it is necessary to vary the pressures of the vapors on the boiling liquid. This cations and requires a tional cost in equipmen introduces many compliconsiderable addit, as it is not only necessary to add compressors but the various pending connections of the syste un turn requires a more increases the In the der relatively highpressures which cxpensivedesign and possibility of leaks.

prior United States patent to Frank m have to be tight in A. Canon and myself, No. 1,614,185, dated January 11, 1927,

reissued as Reissue No. 16,824, December 20, 1927 and in the coapplications of Frank A. Canon and myself, Serial Nos. 569,734,

159,677 and 67,685, We have described the control of catalytic reactions by the use of alloys such as for example,

the boiling point under of mercury,

alloys ordinary atmospheric pressure being varied by the relative proportions of the alloy. Thus, for example, in the case of" the components of a typical alloy such as that of mercury and cadmium, which has been described in the applications above referred to, the boiling point increases with incr cadmium and in order eased percentages of to provide for difthe composition of cations and patent,

equipment and pressure-tight joints are elimmated, it is subject to the disadvantage that for certain purposes where the temperature may require variation from day today, it is a somewhat difficult matter to change the proportion of the various components of the alloy 'in order to bring about the desired change in boiling point.

The present invention combines all of the advantages of the process of my joint prior applications and patent and in addition presents the important advantage that the proportions of the components in the boiling liquid can be continuously varied within wide limits during operation of the system. It is therefore not necessary at any time to shut down operation in order to change the boiling alloy bath and predetermined temperature variations can be' obtained" continuously and simply. The present invention therefore combines, with the advantages of my joint prior applithe only advantage which the pressure system possesses, namely, the possibility of continuous variation of the boiling point without shutting down or interrupting operation. This advantage of the pressure system is obtained without any of the disadvantagesof pressure.

The invention is particularly applicable to high boiling mixtures such as metal alloys but it is also applicable to other mlx- 'tures, such as, for example, solutions of solid materials. j

According to the present invention the composition of the bath is varied by removing or adding components to the condensed vapors of the boilingbath which, in ordinary installations are condensed in a reflux condenser and returned to the bath. The invention will be described in connection with metal alloys for which it is particularly suitable but it should be understood that it is also applicable to solutions of certain solids in liquids which, for purpose of the present invention, possess many of the operating characteristics of alloys or other liquid mercury for the control of the boiling' ATET ()FICQ mixtures in which one of the components is normally a solid.

For example, when a mercury cadmium alloy containing 75% mercury and cadmium and having a boiling point of about 400 C. is used in a catalytic converter, the vapors which are .given off when the mixture boils and which are normally condensed in a reflux condenser and returned have a composition in which the low boiling mercury is present in much higher percentage than in the boiling bat-h itself. If therefore, it is desired to increase the temperature at which the bath boils, this may be effected by drawing off some of the condensed vapors from the reflux condenser. Since the condensed vapors thus removed. are much richer in mercury than the bath itself, the relative amount of "mercury therein decreases and correspondingly the boiling point increases. If it is then again desired to lower the boiling oint this can be eifected by introducing a ditional amounts of liquid mercury into the reflux condenser or into the bath itself. By this simple means a control can be effected throughout a moderate range of concentration. Where higher percentages of cadmium are required than can be readily obtained by this method, a cadmium mercury alloy richer than that present in the bath can be introduced into the reflux condenser and thence into the bath, thus still further increasing the percentage of cadmium. Cadmium can also be removed from the bath by withdrawing the condensate from the reflux condenser, which condensate contains a small amount of cadmium, and continuously replacing it with pure mercury. In general, I find that it is simaler and easier to eflect, the major portion of the control by the addition or subtraction since alloys as the latter is easier to handle high in cadmium possess rel melting points and therefore of mercury,

atively high involve somewhat greater diflieulties in handling. The invention may, of course, be applied to'boiling mixtures in which a normally solid material is for example, aqueous solution of readily soluble salts. In such cases, the boiling water vapors can be partially drawn off or addi tional water can be added. to vary the boiling point continuously during operation.

The referred embodiments of the invention will be escribed in greater detail in connection wit the accompanying drawings, in which various catalytic converters are illustrated. It should be, of course, understood that these are illustrations of only one field in which the present invention is of predominant importance and it can be used in any other field where an accurate regulation of temperature is necessary or p desirable and the invention is in no sense to be consldered as limited to the apparatus dissolved in a liquid,

described in the drawings or to the precise is therein utilized.

In the drawings:

Figure 1 is a cross section through a converter of common type provided with means for removing or adding mercury from the condensed vapors;

Figure 2 illustrates a similar sectional view of a converter provided with means for introducin mercury 01' cadmium into the bath at wil Figure 3 illustrates a similar type of converter provided with means for introducing cadmium alloys of relatively high melting point into the bath during operation;

Figure 4 illustrates a converter of somewhat difierent design having a similar provision for introducing concentrated cadmium alloys; I

- Figure 5 illustrates a liquid heater for thed cracking of oils and similar purposes; an

Figure "6 is a horizontal section taken along the line 6-6,

In the embodiment. shown in Figure 1, a. tubular converter consisting in shell 1, top piece 2, bottom piece 3 and catalyst tubes 4, is provided with a bath which may, for example, be composed of a cadmium and mercury alloy. The level of the bathis considerably above the catalyst in the tubes and a vapor space is provided which is connected through the pipe 5 to the chamber 6 which is in communication with a reflux condenser 7 and a mercury storage tank 8 provided with the valves 9 and 10. A second mercury storage tank 11is connected to the lowest point of the pipe provided with a valve 12.. The tank 11 is also further provided with a drain valve 13. A pipe 14 extends from the bottom of'the shell 1 and is provided with the equalizing. leg 15. A valve 16 is interposed'between the converter and the leg 15 and a drain pipe 17 is further provided. The can be kept molten by the small burner 18.

In operation, after the bath has been heated up by means of the burner 18 the gases for the catalytic reaction which may, for example, consist in vapors of naphthalene and air pass in through the top piece 2, down through the tubes 4 and out through the bottom piece 3, reacting in the presence of the catalyst to form phthalic anhydride. The bath boils and vapors rich in mercury flow up through the pipe 5 and chamber 6 into the reflux condenser '7, where they are condensed, and flow back into the converter. The valves 10 and 12 are closed. If it is desirable for example, to raise the boiling temperature by decreasing the relative proortion ofmercury in the bath the valve 12 a portion of the condensed can be opened and to flow into the tank 11 vapors permitted material in the leg until the percentage of mercury in the converter has fallen to the desired point and correspondingly the boiling point is-raised. If thereafter it is desired boiling point of, the bath, mercury from the tank 8 can be caused to flowinto the .chamber 6 by opening the valve 10 and thence through the pipe 5, back to the bath, again increasing the proportion of mercury 10 therein. I

'The range of temperature control depends, I of course, upon. the amount by which the 1 level of the bath can be lowered, i. e.,tl1e amount of mercury that can be removed. -This is shown in the drawings by'the light dotted lines indicating the highest level of the mercury. The lowest'lev'el of the bath which should usually be sufiicient to cover the catalyst tubes to a height at least as great as that occupied by the catalyst, is shown by dotted lines in dark shading. When the converter is charged in the beginmng, of course, mercury and-solid cadmium may be filled into the leg15 and melted by means or the .burner 18.

In the installation shown in Figure 2, similar portions of the converter are given similar numerals. The converter is of substantially the same type except that baflles 19 are provided to efl'ect a more satisfactory mixture of the reaction gases, and the burn-' er on the expansion leg has been omitted. i

l of converter in which the bath is in tubes 4 The reflux condenser 7- instead of passing into a chamber 6, directly enters the pipe 5- which is connected 'atits lowest point to mercury storage tank 11, as in the construction shown in Figure 1. The pipe 5 beyond the connection with the reflux condenser 7 "passes into a jacketed chamber 20 provided two pipes 23 and 24 .provided with valves 25 and 26 and connecting with a mercury stora e tank 27 and a cadmium storage tank 28. admiumand mercury. in any desired proportion can be caused to flow into the chamber 20 and can be'sufliciently heated by the jacket and heating coil so that alloy thus formed is liquid. By this means an alloy which maybe rich in cadmium or rich in mercury can-be added'at' will to the bathin the converter where it is desired to increase the concentration of'cadmium beyond that readily obtainable by" drawing ofl a proportion of the mercury vapors condensed.

In Figure 3 the converter is of the same general type as that shown in Figures 1 and 2, but is not provided with any drawofi leg 15. The vapors from the bath pass .up through a central pipe 29 which is exposed to the in-coming cold reacting gases and a certain amount ofcondensation there vforetakes place directly in this pipe. The

remaining vapors pass into the top of a chamber 30 which 1s connected;at its lower to again lower the,

with a shut-off valve 21 anda heating coil, 22. In the top of this chamber are mounted the pipe 29 through a pipe 31 pro bath pass up through the pipe 29 and enter the chamber 30 either through this ipe' or through the pipe 31, being condense either in the chamber-orfin the reflux condenser 7 and flow back through the pipe 31.. If it is desired to raise the temperature of the bath the valve 32 is closed and the valve 37 is opened and mercury content in the converter is reduced to thedesired extent. If the concentration of cadmium is to be further increased the valve 37 is closed, and the valves 32 and 34 are opened. Cadmium then flows intd'the chamber 30, is then brought in contact; with the hot condensed mercury from the reflux condenser 7, and is gradually melted or-dissolved by the-latter to form a molten alloy which flows back through the pipe 31. This obviates the necessity of a special heating meaps for keeping the alloy molten, as is' shown in Figure 2 and for some purposes is a more advantageous construction. 4

Figure 4 shows a somewhat different type extending into the catalyst which surrounds them. The upper portion of the converter forms a bath chamber 38 separated from the catalyst space by the partition 39. Ream-- tion gases enter below this'partitlo'n through in the tubes 4v lThe reacting gases are theretion with the vapors "surrounding the upper portion of the catalyst tubes.

from the boiling bath pass up through the the pipe 40 and serve to cool the bath liquid Hill The vapors pipe 29 intoa chamber 30 which isof the I same design as that shown in Figure 3, similar partsv bearing similar numerals. The operation of the converter 1s, of course, s1m1- lar to that of Figure 3 and possesses the same I be introduced into the converter through the flanged filling advantages. Catalyst may pipe 41.

Figures 5 and 6 illustrate a liquid heater for cracking oils or the like. The heater.

consists in a bath container 42 containing an alloy bath 43 in which a continuous pi e 44 is arranged in a zagz ag form in severa layers. This pipe connects with a preheater coil 45 and a pipe line 46 leading from a reser'voi'rof oil to be cracked, or similar products. From the'top of the heating pipe 44 a pipe 47 extends into a heated vaporizing chamber 48 terminating in-a spray 49. The vapor pipe 50 permits the escape ofvvapors usually is considerably less. Part of the oil 'ing temperature to bath. vaporized oil then passesout through the 1.50 the best results.

from the chamber 48 and liquid'from the bottom of this chamber can be Withdrawn through a pipe 51. The whole still-is heated by means of a coalfire or any other suitable method, the greatest temperature being directed against the bottom of: the bath chamber 42. The partly cooled heating gases then pass in series over the preheating coil and around the vaporizing chamber 48.

The chamber 42 is provided with a vapor space which connects to a reflux system which is substantially the same as that shown in Figure 4, similar parts bearing the same reference numerals as ,in the abovementionfed figure. The temperature in the bathf 43-is maintained constant by the boilrefluxing of the vapors. The composition of the vbath can be varie as described in connection with Figures 3 and'4 by the addition of more or less volatile components. r I,

lVhen the still isntosbe operated as an oil cracking still the oil to .be crackedis introduced through the pipe ing coil 45 where it is heated up-to the. desired temperature and then passes through the: heater pipe 44 immersed in the bath where it can be craekedat a-definitely predetermined temperature which is automatically maintained constant by the boiling The heated and partially cracked or ing of the bathand pipe 47 and'is sprayed through the head 49 into the chamber 48 in whic the pressure may be the same as in the cracking coilbut the vapors being drawn oil through .the pipe 50 and the 'unvaporized oil being removed through the pipe 51. Obviously, of course, the chamber can be connected to suitable fractionating heads in ormay vaporize,

.der to efi'ect any desired fractionation of the 12 cracked products.

The still shown in Figures 5 and 6 permits an extraordinarily uniform hi h erackbe maintaine in. the This is of great advantagewhere an accurate control of the cracking temperature is necessary to bring about There is little, if any, tend fency to carbonize in the pipes, as they are cracking pipes 44.

:not exposedto the direct flame and are kept at a uniform temperature which has been determined in advance for the best results.

The "installation, protected as it is against direct flame, also it is not subjected 'to.v extremes of tempera ture which would tend to warp the pipe and set up undesirable strains.

For some purposes the heat on the bottom of the chamber 42 may be sufiicient but where a greater heat is desirable thiscan be efi'ected by passing some of the heating gases around the chamber42. A space 52 is provided for this purpose. 1

46 into the preheatis less liable to breakage as contrary, is applicable to a wide number of different designs ot'iconverters or other devices, in which an accurate regulation of temperature is required. The proper structural design of the installations in every case will be chosen by a competent engineer.

The invention has been described particularly in connection with a mercury and cadmium alloyfor use in cooling converters for d the oxidation of aromatic compounds, such as naphthalene to phthalic anhydride, anthracene to" anthraquinone and the like. Other metal alloys, of course, may be used and in inany cases are advantageous. The particular alloy to be chosen will, of course, depend on the temperature which is required. In some cases binary alloys are preferable and in other cases ternary alloys or alloys containing a still larger number of components may be preferable. A few representative alloys are shown. in the accompanying table and illustrate the possibilities of utilizing the present invention. to readily obtain wide variationsin temperature.

Table 1.

a: coowonqucam assesses;

While for many purposes metal alloy baths arethe most satisfactory temperatureregulating systems for use at relatively high temperatures, certain solutions of solid materials in water or other liquids are important. The following table shows the boiling point of certain representative solutions and the control, of course, can be effected as described in con ection with metal alloys, the

solid material being handled in the same manner as the solid cadmium and the liquid,- ofcourse, takingjheplace of the mercury.

- Table 2.

N HlNOfl KOH CaCh Parts Parts Partgo er 100 er 100 er 1 parts parts parts H2O H O 1 120 o o o 101 10 105 20. 5 101 6.0 103 30 140 92. 5' 110 41. 5

LiCl KCzHaOz Parts er Parts per B. P 100 parts B. P 100 parts i H1O I 12120 In general, the present invention makes it readily possible to continuously control the relative composition of mixtures or solutions in which one of the components may be; liqaid at ordinary temperatures, whereas the the composition other is solid at ordinary temperatures or is relatively non-volatile. The invention can be applied in many fields and is not to be considered as limited to the few representative embodiments which have been described.

l/Vhat is claimed as new is 1. A method of varying the boiling poin of two-phase, liquid-vapor temperatureregulating systems in which the liquid phase contains a plurality of components at least one of which is normally solid and which system includes reflux condensing means for the vapor phase, which comprisesvarying of the reflux condensate before returning the latter to the main body of the liquid phase of the system.

2. A method of raising the boiling point of two-phase, liquid-vapor temperatureregulating systems in which the liquid phase contains a plurality of components at least one of the components being solid at ordi-wf nary temperatures and relatively nonvolatile and which system includes reflux condensing means for the vapor phase, which comprises abstracting a portion of said reflux condensate which is richer in the v volatile components of the liquid phase of 1 point of 'a two-phase,

of a two-phase, regulating system employing a metal allow at least one component Y and is volatile components of the alloy,

and which system includes reflux means for condensing the vapor phase, which, comprises varying the composition of said reflux condensate before the latter is returned to the main body-of liquid in the system.

4. A method of raising the boiling point liquid-vapor temperaturein its liquid phase, of which is a solid at ordinary temperatures relatively less one of the other components and which system is provided with reflux condensing ineans for the vapor phase, which comprises abstracting at least partof said reflux oon densate which is relativelyricher in the whereby the percentage of relatively non-volatile components of the alloyin the main liquid portion of the system is increased. I

5. A method of var ing the boiling point of two-phase, .liqui -vapor temperature regulating systems, utilizing mercury a lays .in their liquid phase and provided with reflux condensing means for the vapor phase, which comprises var ing .the percen age composition of the ref; v returning the latter to the main body, of the liquid in the system. v '1 6. A method of raising the boiling point of a two-phase liquid-vapor temperatureregulating system utilizing a mercury alloy in the liquid phase and provided with reflux volatile than at least ux condensate be ore means for condensing the vapors, which" comprises abstracting at least a portion of the reflux condensate which is relatively richer in mercury than inthe other components of the bath, wherebythe relative percentage of these other components is increased; a

, "7. A method of controlling the boiling point of a two-phase, liquid-vapor temperature-regulating system, utilizing an alloy of mercury and cadmium and provided with reflux means for condensing the vapor phase, which comprises varying the compositlon of the reflux condensate.

8. A method of raising the boiling point' of a two-phase, liquid-vapor temperatureregu'lating system, utilizing an alloy of mercury andcadmium in its liquid phase andprovided with reflux condensing means, which comprises abstracting at least part of the reflux condensate richer in meroury than the main bodv of liquid in the system, percentage of cadmium in the latter is increased; I

9. A two-phase, liquid-vapor temperatureregulating device comprising in combination anobject to be maintained at constant temperature, a container for a liquid bath. so positioned with respect to the object that the bath is in heat-exchanging relation therewith, a vapor spac\e in said liquid container,

which is relatively I whereby the relative catalyst chamber, an

nected to said vapor space,

a reflux condensing means associated with said vapor space, means including a chamber, means for 1ntroducing solid material into said chamber, and means for causin part at least of the vapors entering the re ux condensing system or condensate formed therein to impinge on said solid material.

10. A catalytic. converter comprising a v enclosed bath in heatexchanging relation with said chamber, said enclosed bath being contained in a bathcontaining space which is provided with a vapor space, a reflux condensing system conmeans for. removing reflux condensate from said system, a chamber associated with said system, means for introducing solid material into said reflux condensing ingbath in heat-exchanging relation therewith, said cooling bath being contained in a space which provides for a vapor space, a reflux condensing system connected to said vapor space, means for removing condensate from said reflux condensingsystem, a chamber in said system, means for draining material from said chamber into the. reflux condensing system, and means for heating the material in said chamber and for maintaining it at an elevated temperature.

Signed at Pittsburgh, Pennsylvania, this 17th day of February, 1927.

CHESTER E. ANDREWS.

liquid 

